Illustrated in U.S. Ser. No. 09/558,538 now U.S. Pat. No. 6,309,787, filed concurrently herewith, the disclosure of which is totally incorporated herein by reference, is a process comprising aggregating an encapsulated colorant with colorant particles, and wherein said encapsulated colorant is generated by a miniemulsion polymerization.
Illustrated in U.S. Ser. No. 08/959,798, pending entitled xe2x80x9cToner Processesxe2x80x9d, the disclosure of which is totally incorporated herein by reference, is a process for the preparation of toner comprising
(i) aggregating a colorant dispersion containing a suitable surfactant with a latex emulsion containing an anionic surfactant, a nonionic surfactant, and a water miscible chain transfer agent, or a nonionic surfactant with chain transfer characteristics to form toner sized aggregates;
(ii) coalescing or fusing the aggregates; and optionally
(iii) isolating, washing, and drying the resulting toner.
Illustrated in U.S. Pat. No. 5,944,650 and U.S. Pat. No. 5,766,818, the disclosures of each application being totally incorporated herein by reference, are cleavable surfactants and the use thereof in emulsion/aggregation and coalescence toner processes.
In U.S. Pat. No. 5,766,817, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of toner comprising
(i) aggregating a colorant dispersion with a latex miniemulsion containing polymer, an ionic surfactant, a cosurfactant, and a nonionic surfactant;
(ii) coalescing or fusing the aggregates generated; and optionally
(iii) cooling, isolating, washing, and drying the toner, and wherein the polymer in the miniemulsion is of a diameter of from about 50 to about 500 nanometers. The miniemulsion processes and the miniemulsions of this patent may be selected for the preparation of the encapsulated colorants of the present invention.
The present invention is generally directed to colorant and toner processes, and more specifically, to processes which select aggregation and coalescence, or fusion of a polymer latex, colorant, such as pigment, dye, or mixtures thereof, and optional additive particles. In embodiments, the present invention is directed to processes which provide toner compositions with a volume average diameter of, for example, from about 1 micron to about 25 microns, and preferably from about 2 microns to about 12 microns, and a narrow particle size distribution of, for example, about 1.1 to about 1.45, both as measured by the Coulter Counter method. The resulting toners can be selected for known electrophotographic imaging and printing processes, including digital processes.
The present invention in aspects thereof is directed to a process for the preparation of toners by generating encapsulated colorant latexes or encapsulated colorants prepared by miniemulsion polymerization, wherein the miniemulsion latex emulsion is preferably submicron in size, of from, for example, about 100 nanometers to about 1,000 nanometers and preferably from about 200 nanometers to about 600 nanometers in volume average diameter, and contains a nonionic surfactant and an ionic surfactant of opposite charge polarity to that of the nonionic surfactant, thereafter heating the resulting mixture at, for example, below about the latex resin glass transition temperature, and more specifically, from about 35xc2x0 C. to about 60xc2x0 C. (Centigrade) to form toner sized aggregates of from about 2 microns to about 20 microns in volume average diameter, and which toner is comprised of polymer, colorant, especially pigment and optionally known toner additive particles, followed by heating the aggregate suspension above about the latex resin, or polymer glass transition temperature, and more specifically, at, for example, from about 70xc2x0 C. to about 100xc2x0 C. to effect coalescence or fusion of the components of the aggregates and to form mechanically stable integral toner particles. The miniemulsion can contain colorant, monomer, water, surfactants, and preferably a cosurfactant, such as an alcohol, an alkane, an ether, an alcohol ester, an amine, an alkyl thiol, a halide, or a carboxylic acid ester, which cosurfactant is preferably inert, nonvolatile, water insoluble, liquid at a temperature of from about 40xc2x0 C. to about 90xc2x0 C., and preferably contains a terminal aliphatic hydrocarbyl group with at least about 10 carbon atoms, and more specifically, from about 12 to about 24 carbon atoms, and mixtures thereof, and more specifically, an aliphatic alcohol with at least about 8 carbon atoms, such as from about 10 to about 25 carbon atoms, and an alkane with from about 10 to about 30 carbon atoms. The cosurfactant primarily functions to reduce the diffusion of monomer out of the monomer droplet and enables relatively stable miniemulsions because, it is believed, of the formation of intermolecular complexes at the oil/water interface. The complexes are believed to be liquid condensed and electrically charged thus creating a low, for example from about 0.5 dyne/centimeter to about 5 dynes/centimeter interfacial tension and high resistance to droplet coalescence.
The microencapsulation of colorant is an important area of research in paint and toner industries. Several benefits generated with encapsulation in accordance with the present invention include (1) improved particle dispersion in a resin matrix; (2) improved mechanical properties; (3) protection of the colorant from outside influences during toner processing; (4) protection of the matrix polymer from interaction with the colorant; and (5) excellent colorant encapsulation and uniform or substantial uniform toner triboelectric charging values, or passivation of the colorant.
With the present invention in embodiments, there is selected an encapsulated colorant generated by miniemulsion polymerization process. Aggregation/coalescence of the encapsulated colorant enable the generation of different color toners with uniform tribocharging. This results in toners with similar charging behavior independent of the colorant type.
The aforementioned toners are especially useful for imaging processes, especially xerographic processes, which usually require high toner transfer efficiency, such as those having a compact machine design without a cleaner, or those that are designed to provide high quality colored images with excellent image resolution and signal-to-noise ratio, and image uniformity.
There is illustrated in U.S. Pat. No. 4,996,127 a toner of associated particles of secondary particles comprising primary particles of a polymer having acidic, or basic polar groups and a coloring agent. The polymers selected for the toners of the ""127 patent can be prepared by an emulsion polymerization method, see for example columns 4 and 5 of this patent. In column 7 of this ""127 patent, it is indicated that the toner can be prepared by mixing the required amount of coloring agent and optional charge additive with an emulsion of the polymer having an acidic or basic polar group obtained by emulsion polymerization. In U.S. Pat. No. 4,983,488, there is disclosed a process for the preparation of toners by the polymerization of a polymerizable monomer in the presence of a colorant and/or a magnetic powder to prepare a principal resin component and then effecting coagulation of the resulting polymerization liquid in such a manner that the particles in the liquid after coagulation have diameters suitable for a toner. It is indicated in column 9 of this patent that coagulated particles of 1 to 100, and particularly 3 to 70, are obtained. The disadvantages of, for example, wide particle size distributions hence classification is usually required resulting in low toner yields, are illustrated in U.S. Pat. No. 4,797,339, wherein there is disclosed a process for the preparation of toners by resin emulsion polymerization, wherein similar to the ""127 patent certain polar resins are selected; and U.S. Pat. No. 4,558,108, wherein there is disclosed a process for the preparation of a copolymer of styrene and butadiene by specific suspension polymerization.
In U.S. Pat. No. 5,561,025, the disclosure of which is totally incorporated herein by reference, there are illustrated emulsion/aggregation/coalescence processes wherein there are selected water phase termination agents, that is chain transfer agents that are not water miscible.
Other prior art that may be of interest includes U.S. Pat. Nos. 3,674,736;4,137,188 and 5,066,560.
Emulsion/aggregation processes for the preparation of toners are illustrated in a number of Xerox patents, the disclosures of each of which are totally incorporated herein by reference, such as U.S. Pat. No. 5,290,654, U.S. Pat. No. 5,278,020, U.S. Pat. No. 5,308,734, U.S. Pat. No. 5,370,963, U.S. Pat. No. 5,344,738, U.S. Pat. No. 5,403,693, U.S. Pat. No. 5,418,108, U.S. Pat. No. 5,364,729, and U.S. Pat. No. 5,346,797; and also of interest may be U.S. Pat. Nos. 5,348,832; 5,405,728; 5,366,841; 5,496,676; 5,527,658; 5,585,215; 5,650,255; and 5,650,256.
Processes for the preparation of spherical toners at coalescence temperatures of from about 100xc2x0 C. to about 120xc2x0 C. are illustrated in U.S. Pat. No. 5,501,935, the disclosure of which is totally incorporated herein by reference.
The appropriate components and processes of the above patents can be selected for the processes of the present invention in embodiments thereof.
It is a feature of the present invention to provide toner processes with many of the advantages illustrated herein.
In another feature of the present invention there are provided simple and economical processes for the preparation of black and colored toner compositions with excellent colorant, especially pigment dispersions, thus enabling the achievement of excellent color print quality, and wherein there are selected encapsulated colorants.
It is another feature of the invention to provide a toner which eliminates the need for flushed pigments.
It is a further feature of the invention to provide a toner wherein the pigment particles can be dispersed in situ in a manner that they are less prone to migrate out of the toner.
A further feature of the invention is to provide a toner with high projection efficiency, such as from about 80 to about 98 percent efficiency as measured by the Match Scan II spectrophotometer available from Milton-Roy, for use in transparencies.
Additionally, it is another feature of the present invention to provide a process for obtaining a full process color set of four xerographic color toners, wherein the four toners are comprised of a cyan toner, a magenta toner, a yellow toner, and a black toner wherein the difference in tribocharging among the different four color toners is, for example, less than about 10 xcexcC/gram, and preferably less than about 5 xcexcC/gram, such as from 1 to about 4.
In a further feature of the present invention there is provided a process for the preparation of toner compositions with a volume average diameter of from between about 1 to about 25 microns, and preferably from about 2 to about 12 microns, and a particle size distribution of about 1.10 to about 1.35, and preferably from about 1.15 to about 1.25 as measured by a Coulter Counter without the need to resort to conventional classifications to narrow the toner particle size distribution, and wherein there are selected encapsulated colorants.
Moreover, in another feature of the present invention there is provided a process for the preparation of toner by aggregation and coalescence, or fusion (aggregation/coalescence) of encapsulated colorant, and additive particles, and wherein the encapsulated colorant is formed from a semicontinuous miniemulsion process, and there is included therein colorant, a cosurfactant, or a hydrotrope, small water soluble molecules with minimum surface activity, such as sodium xylene sulfonate or sodium toluene sulfonate, which can be selected to enhance latex polymer stability and reduce the amount of undesirable sediment, and wherein there results an encapsulated colorant dispersion that can be aggregated with colorant particles.
In yet another feature of the present invention there are provided toner compositions with low fusing temperatures of from about 120xc2x0 C. to about 180xc2x0 C., and which toner compositions exhibit excellent blocking characteristics at and above about 45xc2x0 C., and wherein there are selected encapsulated colorants.
These and other features of the present invention are accomplished in embodiments by the provision of toners and processes thereof. In embodiments of the present invention, there are provided encapsulated colorant processes for the preparation of toner compositions by the aggregation/coalescence of the colorant encapsulated by a polymer in the presence of a cosurfactant, and wherein the temperature of the aggregation may be selected to control the aggregate size, and thus the final toner particle size, and the coalescence temperature and time may be utilized to control the toner shape and surface properties.
Aspects of the present invention relate to a process for the preparation of an encapsulated colorant comprising the emulsion polymerization of a miniemulsion of monomer, colorant, ionic surfactant, cosurfactant, and optional nonionic surfactant, and wherein the resulting encapsulated colorant containing a polymer shell is of a diameter of from about 100 to about 1,000 nanometers; a process wherein the diameter is from about 200 to about 600 nanometers, the encapsulated colorant containing a polymer shell is aggregated below about the polymer glass transition temperature, followed by coalescing or fusing of the aggregates above about the polymer or resin shell glass transition temperature, and wherein there results a toner with a size of from about 2 to about 20 microns in volume average diameter; a process wherein the temperature below the polymer shell glass transition temperature is from about 25xc2x0 C. to about 60xc2x0 C., and the heating above the polymer shell glass transition temperature is from about 60xc2x0 C. to about 100xc2x0 C.; a process wherein the temperature below the glass transition temperature is from about 35xc2x0 C. to about 55xc2x0 C., and the heating above the glass transition temperature is from about 70xc2x0 C. to about 95xc2x0 C.; a process wherein the temperature at which the aggregation is accomplished controls the size of the aggregates, and wherein the toner size is from about 2 to about 12 microns in volume average diameter, and wherein the temperature and time of the coalescence or fusion of the components of aggregates control the shape of the resultant toner; a process wherein the aggregation temperature is from about 45xc2x0 C. to about 55xc2x0 C., and wherein the coalescence or fusion temperature is from about 80xc2x0 C. to about 95xc2x0 C.; a process wherein the cosurfactant is selected from the group consisting of alkanes, hydrocarbyl alcohols, ethers, alkyl thiols, amines, halides, and esters, and wherein the cosurfactant optionally possesses from about 10 to about 24 carbon atoms; a process wherein the cosurfactant is an alkane with from about 10 to about 24 carbon atoms, and wherein the alkane is present in an amount of from about 0.05 to about 5 weight percent based primarily on the amount of monomer; a process wherein the cosurfactant is an alcohol, or an alkyl thiol; a process wherein the alcohol contains from about 8 to about 20 carbon atoms; a process wherein the alcohol is decanol, lauryl alcohol, tetradecanol, cetyl alcohol, or octadecanol; a process wherein the alcohol is present in an amount of from about 0.1 to about 5 weight percent; a process wherein the cosurfactant is an alkane of n-decane, dodecane, tetradecane, hexadecane, octadecane octyne, dodecyl cyclohexane, or hexadecyl benzene; a process wherein the alkyl thiol contains from about 10 to about 18 carbon atoms; a process wherein the alkyl thiol is decanethiol, 1 -dodecanethiol, t-dodecanethiol, or octadecanethiol; a process wherein the alkyl thiol is present in an amount of from about 0.1 to about 5 weight percent; a process wherein the colorant is a pigment; a process wherein the aggregates are formed in the presence of a cationic surfactant; a process wherein the aggregation is accomplished at a temperature of from about 15xc2x0 C. to about 1xc2x0 C. below the Tg of the polymer shell for an optional duration of from about 0.5 hour to about 3 hours; a process wherein the coalescence or fusion of the components of aggregates for the formation of integral toner particles comprised of colorant and polymer binder is accomplished at a temperature of about 85xc2x0 C. to about 105xc2x0 C. for a duration of from about 1 hour to about 5 hours; a process wherein the polymer formed is selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(alkyl methacrylate-2-carboxyethyl acrylate), poly(styrene-alkyl acrylate-2-carboxyethyl acrylate), poly(styrene-alkyl acrylate-acrylonitrile-2-carboxyethyl acrylate), poly(styrene-1,3-diene-acrylonitrile-2-carboxyethyl acrylate), and poly(alkyl acrylate-acrylonitrile-2-carboxyethyl acrylate), wherein the polymer is optionally present in an amount of from about 80 percent by weight to about 99 percent by weight of toner; a process wherein the polymer shell is poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), or poly(styrene-alkyl acrylate-2-carboxyethyl acrylate); a process wherein the polymer shell and the toner polymer is selected from the group consisting of poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), and poly(butyl acrylate-isoprene); poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylononitrile), poly(styrene-butyl acrylate-acrylononitrile-acrylic acid), poly(styrene-butadiene-2-carboxyethyl acrylate), poly(styrene-butadiene-acrylonitrile-2-carboxyethyl acrylate), poly(styrene-butyl acrylate-2-carboxyethyl acrylate), and poly(styrene-butyl acrylate-acrylononitrile-2-carboxyethyl acrylate); a process wherein the polymer shell and the toner polymer are poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-2-carboxyethyl acrylate), or poly(styrene-butadiene-acrylic acid); a process wherein the ionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium dodecylnaphthalene sulfate, and sodium tetrapropyl diphenyloxide disulfonate; a process wherein the colorant is carbon black, magnetite, cyan, yellow, magenta, and mixtures thereof; a process wherein the toner particles isolated are from about 2 to about 10 microns in volume average diameter, and the particle size distribution thereof is from about 1.15 to about 1.30, wherein each of the surfactants utilized represents from about 0.01 to about 5 weight percent of the total reaction mixture, and wherein there is optionally added to the surface of the formed toner metal salts, metal salts of fatty acids, silicas, metal oxides, or mixtures thereof, each in an amount of from about 0.1 to about 10 weight percent of the obtained toner particles; a process wherein the solids of the miniemulsion of monomer, colorant, and surfactants is of a diameter of from about 200 to about 600 nanometers; a process for the preparation of toner which comprises
aggregating a component comprised of a colorant core and a polymer shell;
coalescing the aggregates generated; and optionally
isolating the toner, and wherein the component is generated by the emulsion polymerization of an emulsion of water, colorant, monomer, ionic surfactant, nonionic surfactant and optional cosurfactant; a process wherein the cosurfactant is present, and the emulsion is a miniemulsion with a size diameter for the solids thereof of from about 100 to about 1,000 nanometers; a process wherein the toner is isolated; a process wherein the toner is isolated, washed, and dried; a process wherein the colorant encapsulated in the polymer shell is prepared by a free radical-initiated aqueous miniemulsion polymerization of a mixture of olefinic monomers, free radical initiator, chain transfer agent, surfactant, cosurfactant, and water, wherein the amount of monomers selected is from about 1 to about 40 weight percent, and the amount of water is from about 59 to about 98 weight percent, based on the total reaction mixture amount; heating at a temperature of between about 45xc2x0 C. to about 90xc2x0 C., wherein the resulting polymer possesses a number average molecular weight of from about 1,000 grams per mole to about 200,000 grams per mole, a weight average molecular weight of from about 5,000 grams per mole to about 500,000 grams per mole, and a glass temperature of from about 40xc2x0 C. to about 120xc2x0 C., wherein the colorant is present in an amount of from about 1 to about 25 weight percent based on the monomer amount, the free radical initiator is selected in an amount of from about 0.1 to about 10 weight percent based on the monomer or monomers amount, the chain transfer agent is selected in an amount of from about 0.5 to about 10 weight percent based on the monomer or monomers amount, the surfactant is selected in an amount of from about 0.1 to about 10 weight percent based on the monomer or monomers amount, the cosurfactant is selected in an amount of from about 0.005 to about 5 weight percent, based on the monomer or monomers amount, the latex polymer emulsion is comprised of from about 1 to about 40 weight percent of monomer particles, and which miniemulsion is of an average diameter of from about 100 nanometers to about 1,000 nanometers, as measured by light scattering technique on a Coulter N4 Plus Particle Sizer; a process wherein the miniemulsion is comprised of water, colorant, and surfactants wherein the ionic surfactant is of a negative polarity, and the cosurfactant and nonionic surfactant are each of a natural polarity; a process wherein polymerization of the monomer is accomplished by heating; a process wherein the heating is at a temperature of from about 45xc2x0 C. to about 95xc2x0 C.;
(i) aggregating a colorant encapsulated polymer from a miniemulsion containing colorant, polymer, an ionic surfactant, a cosurfactant, and a nonionic surfactant;
(ii) coalescing or fusing the aggregates generated; and optionally
(iii) cooling, isolating, washing, and drying the toner, and wherein the colorant encapsulated latex polymer in the miniemulsion is of a diameter of from about 100 to about 1,000 nanometers; a process wherein the aggregating is below about the polymer shell glass transition temperature, the coalescing or fusing of the aggregates is above about the polymer glass transition temperature, and wherein the colorant encapsulated polymer particle diameter is from about 200 to about 600 nanometers, and there results a toner with a size of from about 2 to about 20 microns in volume average diameter; a process wherein the temperature below the glass transition temperature is from about 25xc2x0 C. to about 65xc2x0 C., and the heating above the glass transition temperature is from about 70xc2x0 C. to about 100xc2x0 C.; a process wherein the temperature below the glass transition temperature is from about 35xc2x0 C. to about 55xc2x0 C., and the heating above the glass transition temperature is from about 70xc2x0 C. to about 95xc2x0 C.; a process wherein the temperature at which the aggregation is accomplished controls the size of the aggregates, and wherein the final toner size is from about 2 to about 10 microns in volume average diameter, and wherein the temperature and time of the coalescence or fusion of the components of aggregates control the shape, such as spherical, of the resultant toner; a process wherein the aggregation temperature is from about 45xc2x0 C. to about 55xc2x0 C., and wherein the coalescence or fusion temperature is from about 80xc2x0 C. to about 95xc2x0 C.; a process wherein the cosurfactant is selected from the group consisting of components of alkanes, hydrocarbyl alcohols, ethers, alkyl thiols, amines, halides, and esters; a process wherein the cosurfactant is an alkane; a process wherein the alkane is n-decane, dodecane, tetradecane, hexadecane, octadecane, and the like, and wherein the alkane is present in an amount of from about 0.05 to about 5 parts; a process wherein the cosurfactant is an alcohol, or an alkyl thiol; a process wherein the alcohol contains from about 10 to about 27 carbon atoms, mixtures thereof and the like; a process wherein the alcohol is decanol, lauryl alcohol, tetradecanol, cetyl alcohol, stearyl alcohol, or octadecanol; a process wherein the alcohol is present in an amount of from about 0.1 to about 5 parts; a process wherein the alkyl thiol contains from about 10 to about 18 carbon atoms; a process wherein the alkyl thiol is decanethiol, 1-dodecanethiol, t-dodecanethiol, or octadecanethiol, and the like; a process wherein the colorant is a pigment, and wherein the pigment dispersion contains an ionic surfactant, and the minilatex emulsion contains a nonionic surfactant and an ionic surfactant of opposite charge polarity to that of the ionic surfactant present in the pigment dispersion; a process wherein the surfactant utilized in the colorant dispersion is a cationic surfactant, and the ionic surfactant present in the latex mixture is an anionic surfactant; a process wherein the aggregation is accomplished at a temperature of from about 15xc2x0 C. to about 1xc2x0 C. below the Tg of the polymer, or latex resin for a duration of from about 0.5 hour to about 3 hours; a process wherein the coalescence or fusion of the components of aggregates for the formation of integral toner particles comprised of colorant, resin and additives is accomplished at a temperature of about 85xc2x0 C. to about 105xc2x0 C. for a duration of from about 1 hour to about 5 hours; a process wherein the shell polymer or coating is selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-2-carboxyethyl acrylate), poly(styrene-1,3-diene-2-carboxyethyl acrylate), poly(styrene-alkyl methacrylate-2-carboxyethyl acrylate), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(alkyl methacrylate-2-carboxyethyl acrylate), poly(styrene-alkyl acrylate-acrylonitrile-2-carboxyethyl acrylate), poly(styrene-1,3-diene-acrylonitrile-2-carboxyethyl acrylate), and poly(alkyl acrylate-acrylonitrile-2-carboxyethyl acrylate), and wherein the polymer is present in an amount of from about 80 percent by weight to about 99 percent by weight of toner, and wherein the colorant is a pigment; a process wherein the polymer is selected from the group consisting of poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylononitrile), poly(styrene-butyl acrylate-acrylononitrile-acrylic acid), poly(styrene-butadiene-2-carboxyethyl acrylate), poly(styrene-butadiene-acrylonitrile-2-carboxyethyl acrylate), poly(styrene-butyl acrylate-2-carboxyethyl acrylate), poly(styrene-butyl acrylate-acrylononitrile-2-carboxyethyl acrylate), and the like, and wherein the polymer is optionally present in an amount of from about 80 percent by weight to about 99 percent by weight of toner, and wherein the colorant is a pigment or a dye; a process wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium dodecyinaphthalene sulfate, and sodium tetrapropyl diphenyloxide disulfonate, and wherein colorant dispersion contains a cationic surfactant of a quaternary ammonium salt; a process wherein the colorant is carbon black, magnetite, cyan, yellow, magenta, and mixtures thereof; a process wherein the toner particles isolated are from about 2 to about 12 microns in volume average diameter, and the particle size distribution thereof is from about 1.15 to about 1.30, wherein each of the surfactants utilized represents from about 0.01 to about 5 weight percent of the total reaction mixture, and wherein there is added to the surface of the formed toner metal salts, metal salts of fatty acids, silicas, metal oxides, or mixtures thereof, each in an amount of from about 0.1 to about 10, and preferably from about 1 to about 3 weight percent of the obtained toner particles; a process wherein the monomer in the miniemulsion is of a diameter of from about 100 to about 1,000 nanometers, or wherein the monomer in the miniemulsion is of a diameter of from about 200 to about 600 nanometers; a process for the preparation of toner which comprises
aggregating an encapsulated colorant with a latex miniemulsion containing polymer of a diameter of from about 100 to about 1,000 nanometers, an ionic surfactant, an optional cosurfactant, and a nonionic surfactant;
coalescing the aggregates generated; and optionally isolating, washing, and drying the toner; toner processes comprised of blending an encapsulated aqueous latex colorant dispersion containing, for example, a pigment, such as HELIOGEN BLUE(trademark) or HOSTAPERM PINK(trademark), and a cationic surfactant, such as benzalkonium chloride (SANIZOL B-50(trademark)), and wherein the latex miniemulsion contains an anionic surfactant, such as sodium dodecylbenzene sulfonate (for example NEOGEN R(trademark) or NEOGEN SC(trademark)), sodium tetrapropyl diphenyloxide disulfonate (for example DOWFAX 2A1(trademark)) and cosurfactant, and wherein the latex polymer is derived from emulsion polymerization of monomers selected, for example, from the group consisting of styrene, acrylates, methacrylates, acrylonitrile, butadiene, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, and the like, thereby resulting in the flocculation of the polymer particles with the pigment particles and optional additives; and which flocculent mixture, on further stirring at a temperature of from about 35xc2x0 C. to about 60xc2x0 C., results in the formation of toner sized aggregates having an aggregate size of from about 2 microns to about 20 microns in volume average diameter as measured by the Coulter Counter (Microsizer II), and a particle size distribution of about 1.15 to about 1.35; thereafter, heating the aggregate suspension at from about 70xc2x0 C. to about 95xc2x0 C. to form toner particles; followed by filtration, washing, and drying in an oven, or the like; processes for the preparation of toner compositions which comprise blending a polymer encapsulated colorant preferably containing a pigment, such as carbon black, phthalocyanine, quinacridone or RHODAMINE B(trademark) type red, green, brown, and the like with a cationic surfactant, such as benzalkonium chloride, wherein the polymer is generated from a minilatex emulsion derived from the emulsion polymerization of monomers selected from the group consisting of styrene, butadiene, acrylates, methacrylates, acrylonitrile, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, and the like, and which latex contains an anionic surfactant, such as sodium dodecylbenzene sulfonate or sodium tetrapropyl diphenyloxide disulfonate, a nonionic surfactant, and a cosurfactant, and which colorant encapsulated latex resin size is, for example, from about 100 to about 1,000 nanometers, and preferably from about 200 to about 600 nanometers as measured by light scattering technique on a Coulter N4 Plus Particle Sizer; heating the resulting flocculent mixture at a temperature below or about equal to the Tg of the polymer or resin formed in the latex, ranging, for example, from about 30xc2x0 C. to about 55xc2x0 C. for an effective length of time of, for example, 0.5 hour to about 2 hours to form toner sized aggregates; and subsequently heating the aggregate suspension at a temperature at or above the Tg of the latex polymer, for example from about 60xc2x0 C. to about 100xc2x0 C., to provide toner particles; and finally isolating the toner product by filtration, thereafter washing and drying in an oven, fluid bed dryer, freeze dryer, or spray dryer; whereby toner particles comprised of polymer, or resin, colorant, and optional additives are obtained.
The colorant encapsulated polymer is preferably prepared by a free radical-initiated aqueous miniemulsion polymerization of a mixture of from about 1 to about 10 monomers, and preferably from about 2 to about 5 monomers, olefinic monomers, free radical initiator, chain transfer agent, surfactant, cosurfactant, and water, wherein the amount of monomer or monomers selected is, for example, from about 1 to about 40 weight percent, and the amount water is from about 59 to about 98 weight percent, based on the total reaction mixture amount by heating at, for example, temperatures of between about 45xc2x0 C. to about 90xc2x0 C., wherein the resulting latex polymer still possesses, for example, a number average molecular weight of from about 1,000 grams per mole to about 200,000 grams per mole, and a weight average molecular weight of from about 5,000 grams per mole to about 500,000 grams per mole, and a glass temperature of from 40xc2x0 C. to about 120xc2x0 C. The colorants selected are present in various effective amounts, such as from about 1 to about 25, and preferably from about 2 to about 14 weight percent based on the total monomer or monomers used to prepare the polymer resin. The free radical initiator is selected in amounts of, for example, from about 0.1 to about 10 weight percent based on the total monomer or monomers selected to prepare the polymer resin. Chain transfer agents are selected in amounts of from about 0.5 to about 10 weight percent based on the total monomer or monomers selected to prepare the polymer resin. Surfactants are selected in amounts of from about 0.1 to about 10 weight percent based on the total monomer or monomers selected to prepare the polymer resin. Cosurfactant is selected in various suitable amounts, such as from about 0.005 to about 5, and preferably from about 0.5 to about 3 weight percent, based on the total monomer or monomers selected to prepare the polymer resin. The latex monomer emulsion is preferably comprised of from about 1 to about 65 weight percent of monomer particles, of average diameter of from about 100 nanometers to about 1,000 nanometers, as measured by light scattering technique on a Coulter N4 Plus Particle Sizer.
With the present invention there is selected in embodiments a colorant encapsulated latex preferably generated by a semicontinuous, miniemulsion polymerization process, followed by aggregation/coalescence of the colorant encapsulated polymer to enable toners with at least four different colors of cyan, yellow, magenta, and black different color toners with uniform tribocharging wherein the difference in tribocharging among the different four color toners is, for example, less than about 10 xcexcC/gram, and preferably less than about 5 xcexcC/gram, such as from about 1 to about 7.
More specifically, with the present invention in embodiments thereof there is selected a semicontinuous, miniemulsion polymerization process to encapsulate colorants and to form colorant encapsulated polymers. Generally, the process of the present invention can be referred to as a miniemulsion polymerization, since the primary colorant particles are dispersed in a monomer or mixture of monomers, with polymerization subsequent to emulsification. The miniemulsion process generates, for example, a water oil emulsion wherein the amount of oil is from about 0.5 to about 80 weight percent, and preferably from about 5 to about 75 weight percent, and the amount of water is from about 20 to about 99.5 weight percent, and preferably from about 25 to about 95 weight percent, based on the total oil and water mixture. Subsequently, the resulting miniemulsion together with initiator can be heated at elevated temperature, for example temperatures of between about 35xc2x0 C. to about 120xc2x0 C., and preferably between about 45xc2x0 C. to about 90xc2x0 C. to accomplish the emulsion polymerization. The encapsulation of colorant particles with the miniemulsion polymerization process offers certain advantages over conventional methods such as the direct dispersion of the particles in the oil medium, rather than in the water phase, by using homogenization in the presence of surfactants. A homogenization is selected to provide a suitable shear to enable the miniemulsion with the colorant particles located inside the miniemulsion droplets. A semicontinuous addition of the miniemulsion to the reactor system will provide excellent stability of the miniemulsion preventing particle coalescence or flocculation among the interactive monomer emulsion droplets, and maintaining particle size in the range of from about 100 to about 1,000 nanometers, and preferably from about 200 to about 600 nanometers, improved latex stability and colorant encapsulation, the amount of colorant being encapsulated within the polymer particle being, for example, from about 80 to about 98 percent, based on the total amount of colorant used for the preparation of the colorant encapsulated latex.
Miniemulsions are relatively stable submicron, for example, about 100 to about 1,000 nanometers dispersions of oil (monomer) in water prepared by shearing a composition containing monomers, water, initiator, chain transfer agent, surfactant, cosurfactant, and additionally, colorant. A principle involved in the preparation of stable miniemulsion, which stability can be maintained by using a cosurfactant, which prevents particle coalescence or flocculation among the interactive monomer emulsion droplets, is the introduction of a low molecular weight, for example Mw of the cosurfactant is not more than about 5,000, preferably not more than about 2,000, and still more preferably from about 100 to about 500, and which cosurfactants are water insoluble to the extent that in water they have a solubility of less than about 10xe2x88x923 grams, preferably less than about 10xe2x88x924 grams, and more preferably from about 10xe2x88x926 grams to about 10xe2x88x924 grams per liter of water to substantially retard the diffusion of monomer and of the emulsion droplet. A cosurfactant usually is comprised of a long chain alcohol or alkane of, for example, at least 10 carbon atoms, and preferably from about 12 to about 24 carbon atoms in length.
The cosurfactant as indicated herein primarily functions to reduce the diffusion of monomer from the monomer droplet, for example the cosurfactant can reduce the monomer diffusion to an extent of about 75 to about 95 percent and enable relatively stable miniemulsions since, it is believed, there is formed intermolecular complexes at the oil/water interface. The enhanced stability in miniemulsions is attributed to the formation of intermolecular complexes at the oil/water interface, which is comprised of solidified bilayers of anionic surfactant and cosurfactant separated by water. The macrostructure of the bilayers is comprised of a tortuous network of irregularly shaped aggregates with diameters between about 5 to about 100 nanometers. The complexes can be considered liquid condensed (the bilayer network separated by water) and the surface charge (zeta-potential) of the miniemulsions is, for example, from about 50 to about 120 mV, and preferably from about 60 to about 100 mV, as determined by the PenKem System 3000 Electrophoresis; and a low interfacial tension, for example from about 0.5 dyne/centimeter to about 5 dyne/centimeter, and high resistance to colorant transport/leaching.
In conventional emulsion polymerization (in the absence of a long chain alcohol or alkane surfactant and/or high shear), the primary mechanisms of particle nucleation are micellar and/or homogeneous nucleation, i.e., the principal locus of particle nucleation is the aqueous phase or the monomer swollen micelles. Monomer droplets ( greater than 1000 nanometers) act as monomer reservoirs supplying monomer to the growing polymer particles. In contrast, miniemulsion polymerizations utilize a surfactant/cosurfactant system to produce small (100 to 1,000 nanometers) monomer droplets. The small droplet size, and consequent large droplet surface area in a miniemulsion results in most of the surfactant being adsorbed to the droplets with little free surfactant available to form micelles or stabilize aqueous-phase polymerization. Hence, there may be little or no micellar or homogeneous nucleation. The droplets become the primary locus of particle nucleation. Particle nucleation in miniemulsion polymerization is predominantly from small monomer droplets stabilized against Ostwald ripening.
Long chain aliphatic mercaptans such as dodecyl mercaptan are commonly used as chain transfer agents to regulate polymer molecular weight in the emulsion polymerization. These mercaptans are usually water-insoluble and could be used as hydrophobes to stabilize the miniemulsion droplets against monomer diffusion and colorant leaching. The miniemulsions stabilized with long chain aliphatic mercaptans are thermodynamically stable. These chain transfer agents may also function as a cosurfactant to stabilize the miniemulsion and the colorant can thus be more easily incorporated into the polymer particles, resulting in homogeneous colorant encapsulated latex composition.
Examples of ethylenically unsaturated monomers include, for example, vinyl aromatic and aliphatic hydrocarbons such as styrene, xcex1-methyl styrene and similar substituted styrenes, vinyl naphthalene, vinyl toluene, divinyl benzene, and vinyl aliphatic hydrocarbons such as 1,3-butadiene, methyl-2-butadiene, 2,3-dimethyl butadiene, cyclopentadiene and dicyclopentadiene as well as ethylenically unsaturated esters such as acrylic, methacrylic, cinnamic and crotonic and the like and esters containing fumaric and maleic type unsaturation, and acid olefinic monomers such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate, sodium acrylate, potassium acrylate, and the like. Particularly preferred monomers include, for example, styrene, 1,3-butadiene, isoprene, alkyl (meth)acrylates such as ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, and 2-carboxyethyl acrylate.
Examples of the polymers formed from the monomers include poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), and poly(butyl acrylate-isoprene); poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylononitrile), and poly(styrene-butyl acrylate-acrylononitrile-acrylic acid), poly(styrene-butadiene-2-carboxyethyl acrylate), poly(styrene-butadiene-acrylonitrile-2-carboxyethyl acrylate), poly(styrene-butyl acrylate-2 carboxyethyl acrylate), and poly(styrene-butyl acrylate-acrylononitrile-2-carboxyethyl acrylate).
Generally, the ethylenically unsaturated ester, styrene functional monomer or other suitable monomer, is from about 75 to about 99 percent by weight of the shell polymer and wherein the polymer is the product of miniemulsion polymerization of monomer and colorant. The olefinic acidic monomer utilized, such as acrylic acid, methacrylic acid or 2-carboxyethyl acrylate, is from about 0 to about 25 weight percent of the polymer resin. For example, the resin could be poly(styrene-butyl acrylate-2-carboxyethyl acrylate).
The free radical initiator utilized is generally an emulsion type water-soluble initiator, such as a persulfate like potassium, sodium, or ammonium persulfate, or oil-soluble initiators, such as benzyl peroxide, lauroyl peroxide, 2,2xe2x80x2-azobis(isobutyronitrile), or 2,2xe2x80x2-azobis-(2-methylbutyronitrile), or mixtures thereof. The free radical is selected in amounts of from about 0.1 to about 10 weight percent based on the total monomer or monomers used to prepare the polymer resin. The chain transfer agents are utilized to adjust the molecular weight of the resin and for adjusting the resin particle to solubilized resin ratio. Chain transfer agents selected include alkylthiol such as 1-dodecanethiol, about 0.5 to about 10 percent on weight, halogenated carbons such as carbon tetrabromide, about 0.1 to about 10 percent on weight, based on the monomer, or monomers used to prepare the polymer resin, or preferably an alkylthiol.
Cosurfactants include, for example, alkanes, and hydrocarbyl alcohols, ethers, amines, halides and esters, which are for example, in instances, inert, nonvolatile, water insoluble, liquids at a temperature of from about 40xc2x0 C. to about 90xc2x0 C., and contain a terminal aliphatic hydrocarbyl group, and mixtures thereof. The terminal aliphatic hydrocarbyl group of at least about 10, and more specifically, from about 10 to about 20 carbon atoms contained therein may be unsaturated, but is preferably saturated, and branched, and is preferably a straight chain. These cosurfactants should be relatively highly water insoluble to the extent that in water they have a solubility of less than about 10xe2x88x923 grams, preferably less than about 10xe2x88x924 grams, and more preferably from about 10xe2x88x926 grams to about 10xe2x88x924 grams per liter of water. The molecular weight Mw of the cosurfactant is, for example, not more than about 5,000, preferably not more than about 2,000, and still more preferably from about 100 to about 500. Examples of specific cosurfactants include alkanes, such as n-decane, n-tetradecane, n-hexadecane, n-octadecane, eicosane, tetracosane, 1-decene, 1-dodecene, 2-hexadecyne, 2-tetradecyne, 3-octyne, 4-octyne, and 1-tetradecene; alicyclic hydrocarbons, such as dodecyl cyclohexane; aromatic hydrocarbons, such as hexadecyl benzene; alcohols, such as decanol, lauryl alcohol, tetradecanol, cetyl alcohol, octadecanol, eicosanol, 1-heptadecanol and ceryl alcohol; hydrocarbyl alcohol esters of lower molecular weight carboxylic acids, such as cetyl acetate; ethers, such as octyl ether and cetyl ether; amines, such as tetradecyl amine, hexadecyl amine, and octadecyl amine; halides, such as hexadecyl chloride and other chlorinated paraffins; hydrocarbyl carboxylic acid esters of lower molecular weight alcohols, such as methyl, ethyl and isoamyl octanoate, methyl and octyl caprate, ethyl stearate, isopropyl myristate, methyl, isoamyl and butyl oleate, glyceryl tristearate, soybean oil, coconut oil, tallow, laurin, myristin, olein and the like. With the processes of the present invention, cosurfactants as illustrated herein are selected, preferably cosurfactants of dodecane, hexadecane, lauryl alcohol, or cetyl alcohol, and which cosurfactant is selected in various suitable amounts, such as from about 0.005 to about 5, and preferably from about 0.5 to about 3 weight percent, or parts based on the monomer, or monomers used to prepare the polymer resin. The cosurfactants increase the stability of the fine-size particle emulsions by inhibiting sedimentation or degradation caused by the tendency of the small particles or droplets to coalescence or diffuse molecularly. The cosurfactants should preferably be inert, and resistant to diffusion into aqueous medium.
Other processes of obtaining polymer particles of from, for example, about 0.01 micron to about 2 microns can be selected from polymer microsuspension process, such as disclosed in U.S. Pat. No. 3,674,736, the disclosure of which is totally incorporated herein by reference, polymer solution microsuspension process, such as disclosed in U.S. Pat. No. 5,290,654, the disclosure of which is totally incorporated herein by reference, mechanical grinding processes, or other known processes.
Various known colorants, such as pigments, present in the toner in an effective amount of, for example, from about 1 to about 20 percent by weight of toner, and preferably in an amount of from about 2 to about 12 percent by weight, that can be selected include carbon black like REGAL 330(copyright); magnetites, such as Mobay magnetites MO8029(trademark), MO8060(trademark); Columbian magnetites; MAPICO BLACKS(trademark) and surface treated magnetites; Pfizer magnetites CB4799(trademark), CB5300(trademark), CB5600(trademark), MCX6369(trademark); Bayer magnetites, BAYFERROX 8600(trademark), 8610(trademark); Northern Pigments magnetites, NP-604(trademark), NP-608(trademark); Magnox magnetites TMB-100(trademark), or TMB-104(trademark); and the like. As colored pigments, there can be selected cyan, magenta, yellow, red, green, brown, blue, or mixtures thereof. Specific examples of pigments include phthalocyanine HELIOGEN BLUE L6900(trademark), D6840(trademark), D7080(trademark), D7020(trademark), PYLAM OIL BLUE(trademark), PYLAM OIL YELLOWS(trademark), PIGMENT BLUE 1(trademark) available from Paul Uhlich and Company, Inc., PIGMENT VIOLET 1(trademark), PIGMENT RED 48(trademark), LEMON CHROME YELLOW DCC 1026(trademark), E.D. TOLUIDINE RED(trademark) and BON RED C(trademark) available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL(trademark), HOSTAPERM PINK E(trademark) from Hoechst, and CINQUASIA MAGENTA(trademark) available from E.I. DuPont de Nemours and Company, and the like. Generally, colored pigments that can be selected are cyan, magenta, red, brown, orange, or yellow pigments, and mixtures thereof. Examples of magentas that may be selected include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as Cl 60710, Cl Dispersed Red 15, diazo dye identified in the Color Index as Cl 26050, Cl Solvent Red 19, and the like. Illustrative examples of cyans that may be used include copper tetra(octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as Cl 74160, Cl Pigment Blue, and Anthrathrene Blue, identified in the Color Index as Cl 69810, Special Blue X-2137, and the like; while illustrative examples of yellows that may be selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as Cl 12700, Cl Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, Cl Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4xe2x80x2-chloro-2,5-dimethoxy acetoacetanilide, and Permanent Yellow FGL. Colored magnetites, such as mixtures of MAPICO BLACK(trademark), and cyan components may also be selected as pigments with the process of the present invention. Colorants include pigment, dye, mixtures of pigment and dyes, mixtures of pigments, mixtures of dyes, and the like. More specifically, pigment examples include Pigment Blue 15:3 having a Color Index Constitution Number of 74610, magenta pigment Pigment Red 81:3 having a Color Index Constitution Number of 45160:3, Yellow 17 having a Color Index Constitution Number of 21105, and carbon black. The pigments selected are present in various effective amounts, such as from about 1 to about 20, and preferably from about 2 to about 12 weight percent of the toner.
The toner may also include known charge additives in effective suitable amounts of, for example, from 0.1 to 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which illustrates a toner with a distearyl dimethyl ammonium methyl sulfate charge additive, the disclosures of which are totally incorporated herein by reference, negative charge enhancing additives like aluminum complexes, and the like. Also, additives to improve flow characteristics and charge additives, if not initially present, to improve charging characteristics may then be added by blending with the formed toner, such additives, including AEROSILS(copyright) or silicas, metal oxides like tin, titanium and the like, metal salts of fatty acids like zinc stearate, and which additives are present in various effective amounts, such as from about 0.1 to about 10 percent by weight of the toner.
Surfactants in effective amounts of, for example, 0.01 to about 15 weight percent of the reaction mixture in embodiments include, for example, nonionic surfactants, such as dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhone-Poulenac as IGEPAL CA-210(trademark), IGEPAL CA-520(trademark), IGEPAL CA-720(trademark), IGEPAL CO-890(trademark), IGEPAL CO-720(trademark), IGEPAL CO-290(trademark), IGEPAL CA-210(trademark), ANTAROX 890(trademark) and ANTAROX 897(trademark) in effective amounts of, for example, from about 0.1 to about 10 percent by weight of the reaction mixture; anionic surfactants such as, for example, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium tetrapropyl diphenyloxide disulfonate, sodium dodecyinaphthalene sulfate, dialkyl benzenealkyl sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN R(trademark), NEOGEN SC(trademark) obtained from Kao, DOWFAX 2A1(trademark) obtained from Dow, and the like, in effective amounts of, for example, from about 0.01 to about 10 percent by weight; cationic surfactants, such as, for example, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C12, C15, C17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL(trademark) and ALKAQUAT(trademark) available from Alkaril Chemical Company, SANIZOL(trademark) (benzalkonium chloride), available from Kao Chemicals, and the like, in effective amounts of, for example, from about 0.01 percent to about 10 percent by weight. Preferably, the molar ratio of the cationic surfactant used for flocculation to the anionic surfactant used in the latex preparation is in the range of from about 0.5 to about 4.
Examples of the surfactant, which are added to the aggregates before coalescence is initiated, can be anionic surfactants, such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN R(trademark), NEOGEN SC(trademark) obtained from Kao, and the like. They can also be selected from nonionic surfactants, such as polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhone-Poulenac as IGEPAL CA-210(trademark), IGEPAL CA-520(trademark), IGEPAL CA-720(trademark), IGEPAL CO-890(trademark), IGEPAL CO-720(trademark), IGEPAL CO-290(trademark), IGEPAL CA-210(trademark), ANTAROX 890(trademark) and ANTAROX 897(trademark). An effective amount of the anionic or nonionic surfactant utilized in the coalescence to primarily stabilize the aggregate size against further growth with temperature is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.5 to about 5 percent by weight of monomers used to prepare the copolymer resin.
Developer compositions can be prepared by mixing the toners obtained with the processes of the present invention with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference, for example from about 2 percent toner concentration to about 8 percent toner concentration. Also, there can be selected as carrier particles, or components a core with a coating thereover of polymethylmethacrylate with a conductive component dispersed therein, such as a conductive carbon black.
Imaging methods are also envisioned with the toners of the present invention, reference for example a number of the patents mentioned herein, and U.S. Pat. No. 4,265,990, the disclosure of which is totally incorporated herein by reference.